Functional perfluoroalkylene organosilicon compounds



United States Patent 3,478,076 FUNCTIONAL PERFLUOROALKYLENE ORGANOSILICON COMPOUNDS Yung Ki Kim and Ogden R. Pierce, Midland, Mich., as-

signors to Dow Corning Corporation, Midland, Mich., a corporation of Michigan No Drawing. Filed Dec. 2, 1966, Ser. No. 598,613 Int. Cl. C07f 7/18; Cllc 3/00 US. Cl. 260-4483 4 Claims ABSTRACT OF THE DISCLOSURE Organosilanes and silanols of the formula ki llm Y -m'SiCH2CHz(CH2CH2)nRrX and siloxanes containing at least one unit of the formula ni llm xmwmomncmcmsro OH; ClzSiCHzCHKC F9200 0 czHi and are examples of such compounds. These silanes and siloxanes are useful as lubricants, laminating resins, elastomers and surface active agents.

CROSS REFERENCE TO RELATED APPLICATION The intermediates for the preparation of the compositions of this invention are described and claimed in the copending application Ser. No. 598,604 of Yung'Ki Kim entitled Fluoroethylene Compounds, filed Dec. 2, 1966. The disclosure of said application being hereby incorporated in this application by reference.

BACKGROUND OF THE INVENTION This invention provides the art with new functional organosilicon compounds in which the fuctions are ester, carboxy, amide, etc. The unique feature being the bridge connecting said functional groups to the silicon atom. The organic functional group is attached directly to a perfiuoroalkylene radical, which in turn, is connected to the silicon through an ethylene spacer. The ethylene spacer stabilizes the compounds to hydrolytic cleavage because fluorine attached to carbon atoms alpha or beta to silicon is unstable.

SUMMARY OF INVENTION This invention relates to compounds of the formula in which Y is a hydrolyzable group or OH, -R" is a monovalent hydrocarbon radical free of aliphatic unsaturation or a ACH CH radical in which A is a perfluoroalkyl radical, m and n each have values of from 0 to 2 inclusive, R, is a perfluoroalkylene radical, X is a radical of the group CONH CEN and COOR in which R is an alkyl radical of 1 to 6 inclusive carbon atoms.

3 ,478 ,076 Ce Patented Nov. 11, 1969 This invention further relates to siloxanes having at least one unit of the formula in which X is COOH, CONH CEN and COOR and R, R n, m and R" are as as above defined, and b has a value from 0 to 2 inclusive, any remaining units in said siloxane being of the formula z.sio

in which Z is a hydrocarbon or halohydrocarbon radical, a hydrogen atom, a Y group or --OH and a has a value from 0 to 3 inclusive.

DETAILED DESCRIPTION OF THE INVENTION The silanes of this invention are best prepared by reacting silanes of the formula Y3 SIH with (I) CH =CH(CH CH ),,R X in the presence of a platinum catalyst such as chloroplatinic acid in the conventional manner for adding SiH compounds to compounds having the terminal OH =CH group. The olefinic' intermediates (I) are prepared in accordance with the description of the aforesaid copending application of Yong Ki Kim.

The silanols of this invention (i.e. where Y is OH) are best prepared by hydrolyzing the corresponding hydrolyzable silanes under neutral conditions by any of the methods well known in the art for the preparation of silanols. The preferred method for preparing such silanols is by the hydrolysis of those compounds in which Y is methoxy.

The siloxanes of this invention can be prepared by two methods. One is by the hydrolysis or cohydrolysis of the above silanes, by conventional means, or by the cohydrolysis of the above defined silanes with silanes of the formula Z,,SiY in which Z, a and Y are as above defined. The particular method chosen for the hydrolysis or cohydrolysis can vary widely depending upon the nature of the substituent groups on the silicon. Hence there are no critical conditions other than the well-known techniques for hydrolyzing and cohydrolyzing silanes.

A second method of preparing such siloxanes is by the addition of compounds (I) supra to siloxanes containing SiH groups in the presence of platinum catalysts. The conditions for carrying out this condition are those normally employed for the addition of SiH containing siloxanes to olefins.

In those siloxanes in which X is a carboxyl group it is preferred that such compounds be prepared by the hydrolysis of the corresponding esters, i.e. hydrolysis of Rllm I ROOCR:(CH2CH2)..CHzCH SiY or of siloxanes containing units of the formula It ll l ROOORr(CH CH2)nCHzOHzSiO 2 In general, better yields of the carboxylic acids are obtained by this method than by attempting to add unsaturated carboxylic acids directly to SiI-I compounds. The hydrolysis of the esters can be carried out in the conventional manner for the hydrolysis of organic esters.

In the compositions of this invention Y can be any hydrolyzable group such as halogen atoms; such as fluorine, chlorine, or bromine; hydrocarbonoxy groups such as methoxy, ethoxy, octadecycloxy, allyloxy, cyclohexyloxy, phenoxy, tolyloxyfbenzyloxy, -'OCH CH OCH and acyloxy groups such as acetoxy, propionyloxy, benzoyloxy, cyclohexoyloxy, and

ketoxime groups such as -ON=C(CH and amine groups such as NH N(CH and sulfide groups such as SCH and the 'nitrile groups, the isocyanate groups, sulfate groups such as sulfonate groups such as carbamate groups such as -OOCNHCH -OOCN(CH in which A is a perfluoroalkyl radical such as CP C F s rr CF21: (CF3) CF and CF3CFZCIZF R, can be any perfluoroalkylene radical such as CF;OF- CFzCF-, CF(|JF and (01%);

CF4F9 CaFts CFa CFa CF2G- R can be any lower alkyl radical such as methyl, ethyl, isopropyl or hexyl.

As can be seen the siloxanes of this invention can be homopolymers or they can be copolymers containing various types of the fluoroalkylene containing siloxane units. When Q represents group the siloxanes of this invention can be represented by the general unit formula QSiO 1'1 RI! Y Q adiom, Q QSiOm and Q l ua or any combination thereof. In addition the siloxanes can contain siloxane units of the formula in which a has a value of from 0 to 3 inclusive. This includes units of the Slog, ZSiO3 2, Z2Si0, Z SiO1 2. Z can be a hydrogen atom, any of the above defined Y groups, a hydroxyl group or any hydrocarbon radical such as any of the radicals specifically shown for R" above, divalent hydrocarbon radicals such as alkylene radicals such as methylene, dimethylene, trimethylene, or tetramethylene; arylene radicals such as phenylene, xenyl ene, tolylene, xylylene or naphthylene; and cycloalkylene radicals such as cyclohexylene and cyclopentylene, Z can also be any alkenyl radical such as vinyl, allyl, hexenyl and butadienyl.

Z can also be any halohydrocarbon radical such as chloromethyl, gamma chloropropyl, bromooctadecyl, chlorocyclohexyl, bromocyclohexenyl, 3-chlorobutenyl-4, chlorophenyl, bromoxenyl, u,u,a-trifluorotolyl, tetrachlorophenyl, p-chlorobenzyl, 3,3,3-trifluoropropy1 and The compositions of this invention are useful for a Wide variety of applications. These include oleophobic coatings, lubricants for metallic parts, elastomers, laminating resins, and surface active agents.

The following examples are illustrative only and should not be construed as limiting the invention, which is properly delineated in the appended claims.

Example 1 To a mixture of 150 g. (.75 m.) of

CH CH('CF COOC H and .75 ml. of chloroplatinic acid in absolute ethanol was added a total of 0.85 mole of methyldichlorosilane as follows: 10 g. of the silane was added and the mixture was stirred and heated. When the temperature reached C. the reaction started and heating was discontinued when the temperature reached C. The remaining silane was then added at such a rate that the temperature was maintained between 110 and C. The entire reaction was carried out in an atmosphere of dry nitrogen.

The crude product was distilled to give the compound C2H5OOC(CF2)2CH2CH2SiC12 the B.P. 120 C. at 20 mm. and refractive index at 25 C. of 1.4065.

Example 2 30 g. of the silane of Example 1 was added with stirring to a mixture of 200 ml. of water and 30 g. of sodium bicarbonate. The reaction was carried out at ice bath temperature. The mixture was taken up in ether and the ether layer was separated, Washed and dried. The solvent was evaporated to give a clear viscous oil which contained silicon-bonded hydroxyl groups, i.e. units of the formula Elle 0211 50 0 0(0 Fz)2CHzCH2s'iO1/3 The oil was mixed with tetra-methyl guanidine acetate and heated under vacuum for 24 hours at 75 to C. Water was removed during polymerization. A viscous siloxane fiuid was obtained which had the unit formula CzHlsOOC(CFzhCHzCHzSiOm Example 3 When the following fluoroalkylene compounds are added to the following silanes in accordance with the procedure of Example 1, the following products are obtained.

7 Example 5 When the siloxane ester CH3 C2H5OOC(CF2)a(CHz)4S iO is hydrolyzed with aqueous HCl under refluxing conditions the siloxane HOOC(CFz)2(CH2)aSiO is obtained. This siloxane can also be obtained by reacting the siloxane ester with an equivalent amount of acetic acid in the presence of a catalytic amount of HCl under conditions where ethylacetate distills from the mixture.

Example 6 u Ya-mS iCH2CH2(CHzCH:)nRrX in which Y is a hydrolyzable group or OH;

R"-is selected from-the'group consisting of alkyl radic a ls Qycloaliphatio radicals, aromatic hydrocarbon radicals, aralkyl radicals, or ACH CH radicals in which A is a perfluoroalkyl radical;

m and n each have values from 0 to 2 inclusive;

R is a perfluoroalkylene radical; and

X is of the group consisting of CONH CEN and COOR' groups in which R is an alkyl radical of from 1 to 6 inclusive carbon atoms.

2. A compound of claim 1 in which n is 0.

3. The compound of claim 1 in which Y is chlorine,

. rm is 1, R" is methyl, n is O, R; is CF CF and X is COOC H v 4. The compound of claim 1 in which Y is chlorine, in and n are both O, R, is CF CF and X is References Cited I STATES PATENTS 2,900,363

8/1959 Bluestein 260-4482 X 3,038,000 6 1962 Schmidt. 3,065,202 ll/l962l Bluestein 260-4482 X 3,112,333 11,/ 1963 B ailey..v 3,128,297 4/1964 Kannervet al.

3,318,843 5/1967 Bluestein 260448.2 X 3,331,813 7/1967 Pittman et al'. 260448.2 X

TOBIAS E. LEVOW, Primary Examiner P. F. SHAVER, Assistant Examiner s. 01. X.R. 25249.6, 351; 260--448.8, 408, 46.5 

